Free Iron Determination in Soil by Flame Atomic Absorption Spectrometry
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摘要:
土壤游离铁是成土母质风化、迁移转化的产物，其形态和活化、老化程度能够反映成土过程和成土环境，可以直接反映土壤的形成环境、形成过程和气候变化。因此，准确测定土壤中的游离铁含量具有重要的现实意义。目前采用紫外分光光度法测定游离铁实验流程长，需要将高价铁还原为低价铁，加之需要显色时间24h，耗费时间长，检测效率较低。本文采用火焰原子吸收光谱法(FAAS)测定土壤中的游离铁含量，系统研究了实验条件对游离铁测定的影响，通过优化样品测定过程中碳酸氢钠的用量、反应温度、反应时间以及清洗次数，确定了称样量为0.5g，加入柠檬酸钠溶液20mL和碳酸氢钠溶液2mL，反应温度75～80℃，反应时间15～30min，再用饱和氯化钠溶液和2mL 1mol/L氯化钠溶液清洗各一次为最佳实验条件。经验证，该方法检出限(3σ)为0.05g/kg，定量限为0.20g/kg，标准曲线线性相关系数为0.9995，方法精密度 (RSD，n=6) 为1.95%～3.76%，标准样品测定误差小于5%，符合土壤调查样品分析测试要求，可推广应用于土壤调查中土壤和沉积物样品分析。
Abstract:Free iron oxide in soil is a product of weathering, migration, and transformation of soil parent materials. Its form, activation, and aging degree can reflect the soil forming process and environment. It is also the main carrier of soil variable charge and an important mineral bonding substance in soil, which can directly reflect the formation environment, formation process, and climate change of the soil. Therefore, accurate determination of free iron in soil has important practical significance. At present, free iron is measured using ultraviolet spectrophotometry. The experimental process for free iron is long, requiring the reduction of high valent iron to low valent iron. In addition, it requires a color development time of up to 24h, which is time-consuming and cannot meet the needs of large-scale sample testing. Flame atomic absorption spectrometry method is used to determine free iron in soil, and the influence of experimental conditions on the determination of free iron is studied. By optimizing the amount of sodium bicarbonate, reaction temperature, reaction time, and cleaning times during the sample determination process, a method for determining free iron in soil is established. The optimal experimental conditions are determined as follows: weigh 0.5g of sample, add 20mL of sodium citrate solution and 2mL of sodium bicarbonate solution, and cleaned once each at a reaction temperature of 75−80℃ for 15min. The detection limit (3σ) of this method is 0.05g/kg, the quantification limit is 0.20g/kg, the linear correlation coefficient of the standard curve is 0.9995, the precision (RSD, n=6) is 1.95%−3.76%, and the standard error is less than 5%, which meets the analysis requirements of soil investigation. It can be widely applied to the analysis of soil and sediment samples in soil investigation.
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表 1 紫外可见分光光度法和火焰原子吸收光谱法测定土壤中游离态铁的检出限比较
Table 1. Comparison of detection limits for free iron in soil by ultraviolet–visible spectrophotometry and flame atomic absorption spectrometry
测定方法 11次空白游离态铁含量测定结果
(g/kg)方法检出限
(g/kg)紫外可见分光光度法 1.23 1.13 1.28 1.44 1.26 1.16 1.03 1.39 1.30 1.22 1.01 0.40 火焰原子吸收光谱法 0.18 0.15 0.18 0.16 0.14 0.15 0.18 0.16 0.17 0.13 0.15 0.05 
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表 2 采用本文方法测定游离铁含量的精密度
Table 2. Precision results of free iron content determined by this study method
样品编号 游离铁含量6次测定值
(g/kg)游离铁含量测定平均值
(g/kg)RSD
(%)1# 27.4 25.6 25.6 24.5 26.4 26.3 26.0 3.76 2# 16.2 16.2 15.8 16.1 16.0 16.8 16.2 1.95 3# 11.2 11.6 11.1 11.5 11.4 12.0 11.5 2.80
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表 3 游离铁含量测定正确度实验结果
Table 3. Accuracy results of of the method for free iron content determination
标准物质编号 游离铁含量7次测定值
(g/kg)游离铁含量测定平均值
(g/kg)游离铁含量标准值
(g/kg)相对误差
(%)GBW(E)070334 41.3 42.6 42.4 42.1 42.4 40.9 41.9 41.9 44±4 −4.72 GBW(E)070339 26.5 27.0 27.5 27.4 27.3 27.1 27.1 27.1 28±3 −3.21 GBW(E)070341 14.2 12.9 13.5 13.8 12.9 13.7 13.5 13.5 13±1.1 3.85
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表 4 采用本文方法分析实际土壤样品游离铁含量测定结果
Table 4. Analytical results of free iron content in actual soil samples determined by this method
实际样品编号 土壤质地 游离铁含量测定值
(g/kg)实际样品编号 土壤质地 游离铁含量测定值
(g/kg)4# 砂土及壤质沙土 16.14 14# 黏壤土 21.92 5# 砂土及壤质沙土 14.57 15# 黏壤土 24.77 6# 黏壤土 25.19 16# 砂质壤土 20.08 7# 砂土及壤质沙土 11.77 17# 砂土及壤质沙土 11.66 8# 砂质壤土 18.28 18# 黏壤土 27.35 9# 砂质壤土 17.97 19# 砂土及壤质沙土 13.61 10# 粉(砂)质黏土 10.07 20# 黏壤土 21.35 11# 黏壤土 20.72 21# 砂土及壤质沙土 13.68 12# 砂质壤土 20.62 22# 砂质壤土 16.42 13# 黏壤土 24.49 23# 黏壤土 23.37
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